CN106380598A - Synthesis method and application of high-polymer ionic liquid - Google Patents
Synthesis method and application of high-polymer ionic liquid Download PDFInfo
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- CN106380598A CN106380598A CN201610897466.5A CN201610897466A CN106380598A CN 106380598 A CN106380598 A CN 106380598A CN 201610897466 A CN201610897466 A CN 201610897466A CN 106380598 A CN106380598 A CN 106380598A
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- guanidine
- hydrochloride
- ionic liquid
- degradation property
- acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
Abstract
The invention relates to a preparation method of a high-polymer ionic liquid and application of the high-polymer ionic liquid. The preparation method comprises the following step: carrying out polycondensation reaction on an organic salt compound and a certain organic monomer to directly prepare the high-polymer ionic liquid. The method has the advantages of fewer preparation steps, simple technique and high yield, and is suitable for industrial production. The high-polymer ionic liquid belongs to a cationic polymer, but can be mixed and dissolved with an anionic surfactant, thereby widening the application range of the cationic polymer. The cationic polymer has the advantages of high bactericidal efficiency, low toxicity and environment friendliness. The high-polymer ionic liquid can be used as an antistatic agent, and can also be used as an electrolyte of the lithium ion battery and supercapacitor. The high-polymer ionic liquid can also be widely used in the field of biology.
Description
Technical field
The present invention relates to technical field of polymer material chemistry, the preparation of specifically one family macromolecule ionic liquid and should
With.
Background technology
In recent years, because ionic liquid is in a liquid state at room temperature, its steam forces down, and dissolubility is good, environmentally friendly and obtain
To widely studied and application.General ionic liquid is made up of organic cation and organic or inorganic anion, molecular weight,
People want to prepare the big degradation property of molecular weight always.Degradation property is that macromolecule intersects with ionic liquid
The product of section, shows the incomparable advantage of small molecular ion liquid, but preparation difficulty is very big.Prepare now macromolecule
The method of ionic liquid has ion liquid polymerization method and macromolecule group ionic liquid method.Ion liquid polymerization method is by ion
Liquid monomer introduces polymerisable group, is then polymerized, obtains degradation property.But a lot of ion liquid polymerizations
Afterwards, room temperature is rendered as solid-state rather than liquid, loses the property of ionic liquid.Macromolecule group ionic liquid method is by ion
Liquid graft, on macromolecule, forms the functional polymer with ionic liquid character, also ratio is larger for the method difficulty, Duo Shuogao
Molecular radical can not be by ionic liquid, and only minority macromolecule is it is achieved which limits its range of application, until current
Only seldom degradation property is produced successfully.The degradation property preparation method starting new simplicity is compeled in eyebrow
Eyelash, the method for the present invention is that organic salt compound and certain monomer are passed through polycondensation reaction, directly prepares macroion
Liquid, can prepare a lot of degradation properties.The method preparation process is few, process is simple, and yield is high, is suitable for industry metaplasia
Produce.Polymerizing cationically has prominent efficient sterilizing, and low toxicity, environmental protection.But polymerizing cationically can not be with anion table
Face activating agent mixing, due to electrostatic interaction, precipitates after mixing, this feature limits polymerizing cationically（As being polymerized guanidine, polymerization
Quaternary ammonium salt）Range of application.The degradation property of present invention synthesis solves the immiscible difficulty of anions and canons activating agent
Topic, can make polymerizing cationically antibacterial extensively apply in field of daily chemicals；This degradation property is also used as
Lithium ion battery and the electrolyte of ultracapacitor；This degradation property extensively can also be applied in biological field.
Content of the invention
Present invention is primarily targeted at providing a class and the miscible degradation property of anion surfactant
Antibacterial, expands cationic polymer range of application.This degradation property synthesis technique is simple, sterilization of high efficiency, cost
Low.
The technical solution adopted for the present invention to solve the technical problems is：
The degradation property that the present invention provides, can be prepared by following methods：Caprolactam and guanidinesalt are in vacuum drying oven
100 degree of drying half an hour, by mol ratio 1:1 caprolactam and guanidinesalt are put in reactor, add a little distilled water, are passed through nitrogen
Air is caught up with only by gas, and nitrogen is protected, and then heats, is warmed up to 100 DEG C, and caprolactam starts to hydrolyze, and starts to be polymerized instead with guanidine
Should, control temperature slowly to heat up, end temperature is 200 DEG C, and in 6 hours response time, polyreaction finishes, and cools to 25 DEG C, from
Completely reacted degradation property is released in hermetic container, standby, under room temperature, degradation property is liquid in flask.
Degradation property is mixed with the solution containing anion surfactant, occurs without precipitation, place 10 days
The above time also occurs without precipitation.Bactericidal effect is not affected by anion surfactant.
Preferably, described guanidinesalt includes：
Guanidine hydrochloride, guanidine sulfate, phosphoguanidine, Guanidine nitrate (1:1), guanidine thiocyanate, guanidine carbonate, guanidine acetate, aminoguanidine monohydrochloride, 1- (4- ammonia fourth
Base) guanidine sulfate, 1- methylguanidine hydrochloride, sulphuric acid aminoguanidine, 6- guanidine radicals hexanoic acid hydrochloride, hexamethylene bis guanidine hydrochloride, oneself
Connection double pungent guanidine, 4- hydroxyl debrisoquine, 1- (5- nitrofurfurylidene) amino guanidine hydrochloride, N- ethyl guanidine hydrochloride, nitrosoguanidine, 3- chlorobenzene
Base guanidine, N- ethyl sulfuric acid guanidine, ten bisguanides, biguanide hydrochlorate, dodine mono-hydrochloric salts, diethyl guanidine sulfate, three ammonia
Base guanidine hydrochloride, an iodobenzene guanidine sulfate, hexa-methylene guanidine hydrochloride, sulphaguanidine, hexa-methylene guanidine phosphate, aminoguanidine carbonic acid
Hydrogen salt, biguanide nitrate, chlorproguanil, methylguanidine, phosphoric acid hydrogen bisguanides, N- (3,4- Dichlorobenzene base) guanidine, polyaminopropyl biguanide, six methylenes
Base -1,6- two cyanoguanidine, Guanidine dihydrogen phosphate, cimetidine, melprex, tricresyl phosphate guanidine, N1 nitroguanidine, sulfonic acid guanidine, hydrochloric acid
Triaminoguanidine, the third guanidine, 1- octyl group guanidine Hemisulphate, hexamethyl proguanil, oxalic acid acylamino- guanidine, acetic acid ten bisguanides, methyl nitroguanidine,
Sad guanidine.
The substitutive characteristics of technical solution of the present invention are between guanidinesalt and caprolactam polycondensation reaction and form polymerization
Guanidinesalt, this polymer can be existed with liquid at room temperature, as polymeric ionic liquid.This kind of synthesis degradation property
Method is with low cost, simple and easy to do, suitable industrialized production.
The degradation property of present invention synthesis is not only used as sterilization bacteriostat in industry, agricultural and daily life
In extensively apply, and can mix with anion surfactant, expand its range of application.It is also used as antistatic
Agent, the electrolyte as lithium ion battery and ultracapacitor, as biomaterial.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
Embodiment 1：
Weigh 1 mole of caprolactam and 1 mole hydrochloride guanidine, 20 grams of distilled water, water and caprolactam, guanidine hydrochloride are sequentially added burning
In bottle, sealed flask, slow heating, it is passed through nitrogen simultaneously into flask, first with nitrogen, air is caught up with only, then proceed to be passed through nitrogen
Gas shielded.Heat while stirring, be incubated 1 hour when temperature is increased to 95 DEG C, continue slowly to increase the temperature to 170 DEG C, then protect
Temperature 1 hour, is warmed up to 190 DEG C and is incubated 2 hours, is finally warmed up to 200 DEG C and is incubated 1 hour, synthesis completes.Then stop heating,
Temperature fall, to 50 DEG C, is released in hermetic container from flask, preserves.
Embodiment 2：
Weigh 1 mole of caprolactam and 1 molar nitric acid guanidine, 30 grams of distilled water, water and caprolactam, Guanidine nitrate (1:1) are sequentially added burning
In bottle, sealed flask, slow heating, it is passed through nitrogen simultaneously into flask, first with nitrogen, air is caught up with only, then proceed to be passed through nitrogen
Gas shielded.Heat while stirring, be incubated 1 hour when temperature is increased to 90 DEG C, continue slowly to increase the temperature to 170 DEG C, then protect
Temperature 1 hour, is warmed up to 190 DEG C and is incubated 3 hours, synthesis completes.Then stop heating, Temperature fall, to 50 DEG C, is put from flask
Go out in hermetic container, preserve.
Embodiment 3：
Weigh 2 moles of caprolactams and 2 mol sulfuric acid guanidines, 50 grams of distilled water, water and caprolactam, guanidine hydrochloride are sequentially added burning
In bottle, sealed flask, slow heating, it is passed through nitrogen simultaneously into flask, first with nitrogen, air is caught up with only, then proceed to be passed through nitrogen
Gas.Heat while stirring, be incubated 1 hour when temperature is increased to 98 DEG C, continue slowly to increase the temperature to 170 DEG C, then it is little to be incubated 1
When, it is warmed up to 190 DEG C and is incubated 2 hours, be finally warmed up to 200 DEG C and be incubated 1 hour, synthesis completes.Then stop heating, naturally drop
Temperature, to 50 DEG C, is released in hermetic container from flask, preserves.
Embodiment 4：
Weigh 1 mole of caprolactam and 1 mole of guanidine carbonate, 30 grams of distilled water, water and caprolactam, guanidine carbonate are sequentially added burning
In bottle, sealed flask, slow heating, it is passed through nitrogen simultaneously into flask, first with nitrogen, air is caught up with only, then proceed to be passed through nitrogen
Gas.Heat while stirring, be incubated 1 hour when temperature is increased to 92 DEG C, continue slowly to increase the temperature to 170 DEG C, then it is little to be incubated 1
When, it is warmed up to 190 DEG C and is incubated 2 hours, be finally warmed up to 200 DEG C and be incubated 1 hour, synthesis completes.Then stop heating, naturally drop
Temperature, to 50 DEG C, is released in hermetic container from flask, preserves.
Embodiment 5：
Weigh 1.5 moles of caprolactams and 1.5 molar acetate guanidines, 30 grams of distilled water, water and caprolactam, guanidine acetate are added successively
Enter in flask, sealed flask, slow heating, it is passed through nitrogen simultaneously into flask, first with nitrogen, air is caught up with only, then proceed to lead to
Enter nitrogen.Heat while stirring, be incubated 1 hour when temperature is increased to 90 DEG C, continue slowly to increase the temperature to 170 DEG C, then protect
Temperature 1 hour, is warmed up to 190 DEG C and is incubated 2 hours, is finally warmed up to 200 DEG C and is incubated 1 hour, synthesis completes.Then stop heating,
Temperature fall, to 50 DEG C, is released in hermetic container from flask, preserves.
Embodiment 6：
Weigh 2 moles of caprolactams and 2.1 mole hydrochloride aminoguanidines, 60 grams of distilled water, by water and caprolactam, GER-11.
Sequentially add in flask, sealed flask, slow heating, it is passed through nitrogen simultaneously into flask, first with nitrogen, air is caught up with only, then
Continue to be passed through nitrogen.Heat while stirring, be incubated 1 hour when temperature is increased to 95 DEG C, continue slowly to increase the temperature to 170
DEG C, then it is incubated 1 hour, it is warmed up to 190 DEG C and is incubated 2 hours, be finally warmed up to 200 DEG C and be incubated 1 hour, synthesis completes.Then stop
Only heat, Temperature fall, to 50 DEG C, is released in hermetic container from flask, preserve.
Claims (6)
1. a kind of degradation property, it is characterised in that number-average molecular weight is more than 5000, is in the range of 0 DEG C 200 DEG C
Liquid.
2. degradation property as claimed in claim 1 is it is characterised in that synthesis material is caprolactam and guanidinesalt（Bag
Include guanidine hydrochloride, guanidine sulfate, phosphoguanidine, Guanidine nitrate (1:1), guanidine thiocyanate, guanidine carbonate, guanidine acetate, aminoguanidine monohydrochloride, 1- (4- ammonia fourth
Base) guanidine sulfate, 1- methylguanidine hydrochloride, sulphuric acid aminoguanidine, 6- guanidine radicals hexanoic acid hydrochloride, hexamethylene bis guanidine hydrochloride, oneself
Connection double pungent guanidine, 4- hydroxyl debrisoquine, 1- (5- nitrofurfurylidene) amino guanidine hydrochloride, N- ethyl guanidine hydrochloride, nitrosoguanidine, 3- chlorobenzene
Base guanidine, N- ethyl sulfuric acid guanidine, ten bisguanides, biguanide hydrochlorate, dodine mono-hydrochloric salts, diethyl guanidine sulfate, three ammonia
Base guanidine hydrochloride, an iodobenzene guanidine sulfate, hexa-methylene guanidine hydrochloride, sulphaguanidine, hexa-methylene guanidine phosphate, aminoguanidine carbonic acid
Hydrogen salt, biguanide nitrate, chlorproguanil, methylguanidine, phosphoric acid hydrogen bisguanides, N- (3,4- Dichlorobenzene base) guanidine, polyaminopropyl biguanide, six methylenes
Base -1,6- two cyanoguanidine, Guanidine dihydrogen phosphate, cimetidine, melprex, tricresyl phosphate guanidine, N1 nitroguanidine, sulfonic acid guanidine, hydrochloric acid
Triaminoguanidine, the third guanidine, 1- octyl group guanidine Hemisulphate, hexamethyl proguanil, oxalic acid acylamino- guanidine, acetic acid ten bisguanides, methyl nitroguanidine,
Sad guanidine）.
3. degradation property as claimed in claim 1 is it is characterised in that caprolactam is 1 with the mol ratio of guanidinesalt：
0.8—1：1.2.
4. degradation property as claimed in claim 1 is it is characterised in that synthesis temperature scope：100 DEG C 200 DEG C, close
The one-tenth time：6 10 hours.
5. degradation property as claimed in claim 1 is it is characterised in that it can be any with anion surfactant
Ratio mixes and occurs without precipitation.
6. degradation property as claimed in claim 1 is it is characterised in that it can serve as antibacterial and antibacterial, it
Can serve as antistatic additive, be used as electrolyte, be used as biomaterial.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746595A (en) * | 2019-11-01 | 2020-02-04 | 吉林师范大学 | Preparation method of poly (propylene glycol) guanidine hydrochloride |
| CN111019121A (en) * | 2019-11-25 | 2020-04-17 | 石家庄学院 | Preparation method of guanidine polymer ionic liquid |
| CN114181389A (en) * | 2021-05-31 | 2022-03-15 | 杭州聚合顺新材料股份有限公司 | Antibacterial nylon 6 containing guanidino group and preparation method thereof |
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| US20130001092A1 (en) * | 2009-11-25 | 2013-01-03 | Andrew Peter Abbott | Ionic liquids |
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| US20130001092A1 (en) * | 2009-11-25 | 2013-01-03 | Andrew Peter Abbott | Ionic liquids |
| CN101941986A (en) * | 2010-07-15 | 2011-01-12 | 华南理工大学 | Y aromatic ligand ionic liquid and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746595A (en) * | 2019-11-01 | 2020-02-04 | 吉林师范大学 | Preparation method of poly (propylene glycol) guanidine hydrochloride |
| CN110746595B (en) * | 2019-11-01 | 2023-12-22 | 吉林师范大学 | Preparation method of poly (propylene glycol) guanidine hydrochloride |
| CN111019121A (en) * | 2019-11-25 | 2020-04-17 | 石家庄学院 | Preparation method of guanidine polymer ionic liquid |
| CN114181389A (en) * | 2021-05-31 | 2022-03-15 | 杭州聚合顺新材料股份有限公司 | Antibacterial nylon 6 containing guanidino group and preparation method thereof |
| CN114181389B (en) * | 2021-05-31 | 2023-07-04 | 杭州聚合顺新材料股份有限公司 | Antibacterial nylon 6 containing guanidine group and preparation method thereof |
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| CN106380598B (en) | 2018-10-19 |
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